CN1732233A - Water-absorbing resin composition - Google Patents

Water-absorbing resin composition Download PDF

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Publication number
CN1732233A
CN1732233A CNA2003801073705A CN200380107370A CN1732233A CN 1732233 A CN1732233 A CN 1732233A CN A2003801073705 A CNA2003801073705 A CN A2003801073705A CN 200380107370 A CN200380107370 A CN 200380107370A CN 1732233 A CN1732233 A CN 1732233A
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Prior art keywords
resin composition
water absorbency
absorbent
absorbent resin
gel
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Granted
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CN100349987C (en
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半田昌良
绳田康博
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Sumitomo Seika Chemicals Co Ltd
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Seitetsu Kagaku Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005Stabilisers against oxidation, heat, light, ozone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/15Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/53Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/30Sulfur-, selenium- or tellurium-containing compounds

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Vascular Medicine (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Engineering & Computer Science (AREA)
  • Biomedical Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Orthopedics, Nursing, And Contraception (AREA)

Abstract

This present invention provides a water-absorbent resin composition comprising an oxygen-containing reducing inorganic salt and a water-absorbent resin, wherein the iron content in the resin composition is at most 1 ppm; an absorbent having the above-mentioned water-absorbent resin composition and a hydrophilic fiber; and an absorbent article comprising the above-mentioned absorbent interposed between a liquid-permeable sheet and a liquid-impermeable sheet.

Description

Water absorbency resin composition
Technical field
The present invention relates to a kind of water absorbency resin composition.Say in more detail, relate to a kind of water absorbency resin composition, used the cartridge and the absorbent commodity of this water absorbency resin composition.Absorbent commodity with headed by the urine absorbing material etc., can suit as civil construction such as filler materials with food fresh keepings such as material, dropping liquid absorption agent, refrigeration agent with material, soil with the agriculture and garden of water-keeping material etc. with article etc. with sanitary materials such as paper nappy, sanitary towel, incontinence pad, pet.
Background technology
Absorbent article such as paper nappy or sanitary towel, normally by the cartridge that constitutes by hydrophilic fibre and absorbent resin, be held on and be configured in the liquid perviousness sheet material of Body contact one side and be configured between the non-perviousness sheet material of liquid of an opposite side and form with it.
In recent years, in order to reach purpose easy to carry and comfortable and easy to wear, cartridge and used the paper nappy of cartridge and sanitary towel etc. has the tendency of attenuation.Along with its attenuation, to bleed back and leak in order when having absorbed big quantity of fluid, also to reduce, people are carrying out all research always, wish to develop amount that has reduced the used hydrophilic fibre of cartridge and the cartridge that has increased the amount of absorbent resin.
But, owing to urinate and wait gel that body fluid generates deterioration in time usually by absorbing the people, so the reduction of the absorptivity of absorbent resin.In addition, the deterioration of gel is further carried out, and absorbent resin itself can part decompose, and therefore water-soluble solute is by stripping in the gel.
Therefore, used the product of this absorbent resin to contact with human body when using, the water-soluble solute of stripping can be attached on the skin, might cause inflammation etc.
And then, in the many cartridges of absorbent resin amount, since between the absorbent resin under the state that is in contact with one another gel generation deterioration, therefore the water-soluble solute of stripping stops up the gap between gel particles, liquid easily takes place to hinder to the phenomenon of absorbent resin infiltration, i.e. so-called " gel blockage ".Described gel blockage is considered to one of reason that takes place the cartridge leakage.
The genesis mechanism of gel deterioration is very complicated, therefore be difficult to determine its reason, but one of its reason is inferred relevant with ferrous components and the ferrous components in the absorbent resin in people's urine.
Therefore, in order to improve the stability of gel, contain the water absorbency resin composition (spy opens clear 63-118375 communique) of oxygen-containing reducing inorganic salt, the water absorbency resin composition (spy opens flat 1-210463 communique) that contains radical chain terminator and metal chelator etc. and be suggested.
But in these water absorbency resin compositions, the absorbent resin amount that contains in cartridge has the shortcoming that can not fully realize gel stability for a long time.
In addition, when absorbent resin is preserved for a long time, partially denaturing can take place, therefore produce painted sometimes in hot and humid atmosphere.Under the painted situation of absorbent resin, use the appearance damage of the cartridge or the absorbent commodity of this absorbent resin, therefore caused value of the product to reduce.Especially in absorbent resin amount many cartridge and absorbent commodity, the painted of absorbent resin easily becomes obvious.
Therefore, wish in recent years the coloring resistance of absorbent resin is improved.The coloring mechanism of absorbent resin, the mechanism that produces deterioration, decomposition with described gel is the same, and is very complicated, therefore is difficult to concrete its painted reason of determining.But one of its reason is inferred relevant with the ferrous components that contains in the absorbent resin.
As the material that the coloring resistance of absorbent resin is improved, it is known to contain the water-absorbent agent composition (spy opens the 2000-327926 communique) of absorbent resin and organic carboxyl acid class and/or its salt, the water-absorbent agent composition (spy opens the 2000-230129 communique) that contains anti-coloring agent and/or antioxidant and/or boron compound etc.
But, in these compositions, in the many cartridges of absorbent resin amount, the shortcoming that can not realize sufficient coloring resistance is arranged.
Therefore, even under the absorbent resin amount that contains in the cartridge situation how, gel is also superior to the stability that the people such as urinates at body fluid, even under hot and humid, the exploitation of water absorbency resin composition, the cartridge that has used this water absorbency resin composition and absorbent commodity that coloring resistance is also superior is expected.
Disclosure of an invention
Even the object of the present invention is to provide under the absorbent resin amount situation how that contains in the cartridge, gel is also superior to the stability that the people such as urinates at body fluid, even and hot and humid following, water absorbency resin composition, the cartridge that has used this water absorbency resin composition and absorbent commodity that coloring resistance is also superior.
The present invention relates to
(1) containing oxygen-containing reducing inorganic salt and absorbent resin and iron level is the following water absorbency resin composition of 1ppm;
(2) further contain the described water absorbency resin composition of organic oxidation-resistant agent;
(3) has the cartridge of described water absorbency resin composition and hydrophilic fibre; And
(4) between liquid perviousness sheet material and the non-perviousness sheet material of liquid, maintain the absorbent commodity of described cartridge.
Detailed description of the invention
One big feature of water absorbency resin composition of the present invention be contain oxygen-containing reducing inorganic salt and absorbent resin, iron level is below the 1ppm.Water absorbency resin composition of the present invention, owing to have such feature, even therefore realized that the absorbent resin amount that contains in the cartridge is many, gel is urinated the people and is waited the stability of body fluid also superior, even and at hot and humid time, the effect that coloring resistance is also superior.
In addition, water absorbency resin composition of the present invention when further containing the organic oxidation-resistant agent, realized not only the people such as is urinated at body fluid, and to aqueous electrolyte liquid, the stability of gel is also superior, even and hot and humid down, the effect that coloring resistance is also superior.
As the absorbent resin that uses among the present invention, can enumerate cross-linking agent, cross-linked isobutylene-copolymer-maleic anhydride, polyacrylic acid part corrective cross-linking agent, vinyl acetate-acrylic copolymer saponified etc. of cross-linking agent, maleic anhydride grafted polyethylene alcohol of cross-linking agent, vinyl alcohol-acrylate multipolymer of hydrolysate of cross-linking agent, the starch-acrylate graft copolymer of acrylate polymer for example.Wherein, because the cross-linking agent of acrylate polymer can absorb a large amount of water, no matter and apply how many loads, the water that absorbs can both be remained on intramolecularly, therefore preferred the use.
The viewpoint of the iron level from the water absorbency resin composition that reduction obtains wishes that the iron level in the absorbent resin is below the 1ppm, to be preferably below the 0.5ppm.
The manufacture method of absorbent resin, no particular restriction.Its representational manufacture method can be enumerated and use the few raw material of iron level, adopts the method for manufacturing absorbent resin such as anti-phase suspension polymerization, water solution polymerization process etc.
In addition, said in this specification sheets " iron level " is meant according to following measuring method the iron level in the sample surveyed periodic value.In the present invention, as sample, specifically use absorbent resin, oxygen-containing reducing inorganic salt, organic oxidation-resistant agent or water absorbency resin composition.
(measuring method of iron level)
Accurately weighing sample 1g puts it in the beaker of 200mL capacity, adds vitriol oil 3mL and concentrated nitric acid 5mL in beaker, makes sample fully dissolve, and the solution that obtains is heated near its boiling point, makes sample decompose.
Then, become transparent until the black liquor that obtains, Yi Bian continue heating Yi Bian under agitation add nitric acid.The liquid that becomes transparent is further heated down at 350 ℃, and evaporation drying reclaims solid substance thus.
After the solid substance that obtains is cooled to 25 ℃, all these solid substances and concentrated hydrochloric acid 1mL are joined in the volumetric flask of 50mL capacity, add distilled water, reach 50mL, be prepared into sample solution until its total amount.
Use atomic absorption analysis instrument [(strain) Shimadzu Seisakusho Ltd. system, model: AA-6700] that the absorbancy of the sample solution that obtains is measured.
In addition, utilize and aforementioned same operation, measure the absorbancy of iron standardized solution, make calibration curve, calculate iron level (ppm) in the sample by this calibration curve.
As the oxygen-containing reducing inorganic salt that use among the present invention, can enumerate for example sulphite such as S-WAT, potassium sulfite, calcium sulfite, zinc sulfite, ammonium sulphite; Hydrosulphite such as sodium bisulfite, Potassium hydrogen sulfite, calcium bisulfite, ammonium bisulfite; Pyrosulfites such as Sodium Pyrosulfite, potassium pyrosulfite, ammonium pyrosulfite; Hyposulfite such as V-Brite B, potassium hyposulfite, ammonium hyposulfite, calcium hyposulfite, zinc dithionite; Trithionates such as potassium trithionate, trithionic acid sodium; Tetrathionate such as potassium tetrathionate, sodium tetrathionate; Thiosulphates such as Sulfothiorine, Potassium Thiosulphate, ammonium thiosulfate; Nitrite such as Sodium Nitrite, potassium nitrite, calcium nitrite, zinc nitrite.Wherein, from the stability of raising gel and the viewpoint of coloring resistance, preferred sulphite, hydrosulphite, pyrosulfite, hyposulfite and the nitrite of using, more preferably use sulphite and hydrosulphite, further preferred S-WAT, potassium sulfite, sodium bisulfite and the Potassium hydrogen sulfite of using.
The viewpoint of the iron level in the water absorbency resin composition that is obtained by reduction is set out, and wishes that the iron level in the oxygen-containing reducing inorganic salt is below the 10ppm, is preferably below the 5ppm, more preferably below the 3ppm.
Set out by the stability that improves gel and the viewpoint of coloring resistance, the amount of oxygen-containing reducing inorganic salt, with respect to absorbent resin 100 weight parts, hope is more than 0.01 weight part, is preferably more than 0.05 weight part.In addition, even used the oxygen-containing reducing inorganic salt of volume, there be not to embody gel stability and the coloring resistance effect that matches with its consumption yet, do not calculate economically on the contrary, and make the iron level in the water absorbency resin composition uprise, so the amount of oxygen-containing reducing inorganic salt, with respect to absorbent resin 100 weight parts, hope is below 5 weight parts, is preferably below 3 weight parts.Therefore, consider these situations, the amount of oxygen-containing reducing inorganic salt, with respect to absorbent resin 100 weight parts, hope is 0.01~5 weight part, is preferably 0.05~3 weight part.
Water absorbency resin composition of the present invention for example can obtain by mixing absorbent resin and oxygen-containing reducing inorganic salt.Its blending means, no particular determination.
As the example of the method for mixing absorbent resin and oxygen-containing reducing inorganic salt, can enumerate in (1) monomer solution before the polymerization that constitutes absorbent resin, add the oxygen-containing reducing inorganic salt and carry out the blended method; (2) in the aqueous gel shape thing of absorbent resin, add the oxygen-containing reducing inorganic salt and carry out the blended method; (3) carry out between dry epoch to absorbent resin or after the drying, in absorbent resin, add the oxygen-containing reducing inorganic salt and carry out blended method etc.In these methods, consider that from viewpoint easy and simple to handle the method for above-mentioned (3) is preferably used.
And the oxygen-containing reducing inorganic salt as the stable harmless words to gel, can use any one form in the powdery and the aqueous solution.If consider the operability when making, the oxygen-containing reducing inorganic salt preferably use powdery.
The mixing machine that uses during as mixing absorbent resin and oxygen-containing reducing inorganic salt can be enumerated for example nauta mixer, ribbon mixer, the rotary mixing machine of intersection, cone-type mixer, twin columns kneading machine, screw type mixer, V-shape mixing machine, W font mixing machine, high-speed transitions continuous mixer etc.But these mixing machines that the invention is not restricted to enumerate.
Iron level in the water absorbency resin composition that contains oxygen-containing reducing inorganic salt and absorbent resin of the present invention that obtains like this becomes below the 1ppm, be preferably below the 0.5ppm, when adjusting iron level like this, can realize satisfied gel stability and coloring resistance.
In addition, among the present invention, in the described water absorbency resin composition, can further contain the organic oxidation-resistant agent.Like this, when in water absorbency resin composition, containing the organic oxidation-resistant agent, can improve the stability of gel for aqueous electrolyte liquid.
The organic oxidation-resistant agent does not have particular determination.As the organic oxidation-resistant agent, can enumerate for example xitix classes such as L-xitix, L-sodium ascorbate, D-xitix, D-sodium ascorbate; Saccharosonic acid such as saccharosonic acid, SODIUM ISOVITAMIN C class; Nutgalls acids such as gallic acid, methyl gallate, Progallin A, gallic acid n-propyl, isoamyl gallate, Stabilizer GA 8, Progallin LA; Protocatechuic Acid such as Protocatechuic Acid, ethyl protocatechuate class; Benzimidazoless such as 2-mercaptobenzimidazole; Alkyl hydroxy methyl-phenoxide classes such as butyl hydroxyanisole, these materials can separately or be mixed use more than 2 kinds.Wherein, from the stable superior viewpoint of gel for aqueous electrolyte liquid, preferred xitix class, saccharosonic acid class, Nutgalls acids, Protocatechuic Acid class, benzimidazoles and alkyl hydroxy methyl-phenoxide class, more preferred xitix class, saccharosonic acid class and Nutgalls acids, further preferred L-xitix, SODIUM ISOVITAMIN C and gallic acid n-propyl.
Iron level in the organic oxidation-resistant agent, the viewpoint of the iron level in the water absorbency resin composition that is obtained by reduction is set out, and wishes to be preferably below the 3ppm for below the 5ppm.
The amount of organic oxidation-resistant agent, by realizing that the abundant stability viewpoint of gel to aqueous electrolyte liquid sets out, with respect to absorbent resin 100 weight parts, hope is more than 0.001 weight part, is preferably more than 0.005 weight part.In addition, even used the organic oxidation-resistant agent of volume, there be not to embody gel stability and the coloring resistance effect that matches with its consumption yet, do not calculate economically on the contrary, and make the iron level in the water absorbency resin composition uprise, so the amount of organic oxidation-resistant agent, with respect to absorbent resin 100 weight parts, hope is below 5 weight parts, is preferably below 2 weight parts.Consider these situations, the amount of organic oxidation-resistant agent, with respect to absorbent resin 100 weight parts, hope is 0.001~5 weight part, is preferably 0.005~2 weight part.
In addition, consider that the preferred usually and oxygen-containing reducing inorganic salt of organic oxidation-resistant agent are used in combination by stability that improves gel and coloring resistance viewpoint.
By mixing absorbent resin, oxygen-containing reducing inorganic salt and organic oxidation-resistant agent, can access the water absorbency resin composition that contains the organic oxidation-resistant agent.Mix the method for these compositions and the interpolation order when mixing, no particular determination.
The example of method that contains the water absorbency resin composition of organic oxidation-resistant agent as manufacturing can be enumerated the method for adding organic antioxidant in (1) monomer solution before the polymerization that constitutes absorbent resin; (2) add the method for organic antioxidant in the aqueous gel shape thing of absorbent resin; (3) carry out between dry epoch to absorbent resin or after the drying, in absorbent resin, add the method for organic antioxidant etc.In these methods, consider that from viewpoint easy and simple to handle the method for above-mentioned (3) is preferably used.
In addition, the organic oxidation-resistant agent can be used any one form in the powdery and the aqueous solution as the stable harmless words to gel.If consider the operability when making, powdery is preferably used in the organic oxidation-resistant agent.
The mixing machine that uses during as mixing absorbent resin, oxygen-containing reducing inorganic salt and organic oxidation-resistant agent can be enumerated for example nauta mixer, ribbon mixer, the rotary mixing machine of intersection, cone-type mixer, twin columns kneading machine, screw type mixer, V-shape mixing machine, W font mixing machine, high-speed transitions continuous mixer etc.But these mixing machines that the invention is not restricted to enumerate.
The iron level that the present invention who obtains like this contains in the water absorbency resin composition of oxygen-containing reducing inorganic salt, absorbent resin and organic oxidation-resistant agent is decided to be below the 1ppm, be preferably below the 0.5ppm, when adjusting iron level like this, can realize satisfied gel stability and coloring resistance.
Among the present invention, use described water absorbency resin composition, body can be absorbed.
Cartridge is the material with water absorbency resin composition and hydrophilic fibre.
For hydrophilic fibre, no particular determination.Example as hydrophilic fibre.Can enumerate cellulosic fibre, man-made cellulose fibers etc.And hydrophilic fibre needs only in the scope that does not hinder the object of the invention, also can contain to have hydrophobic synthon.
In order to improve the form retentivity of cartridge, in the cartridge of the present invention, can add tackiness tackiness agents such as hot melt viscosity synthon, Hotmelt Adhesive, tackiness emulsion.
The content of the water absorbency resin composition in the cartridge is set out by body fluid such as abundant absorption urine, the viewpoint of giving comfortable wearing feeling, is preferably more than the 40 weight %, more preferably more than the 50 weight %.In addition, the content of the water absorbency resin composition in the cartridge when making it contain hydrophilic fibre or tackiness tackiness agent in order to improve the form retentivity of the cartridge that obtains, to consider, is preferably below the 95 weight %, more preferably below the 90 weight %.Consider these situations, the content of the water absorbency resin composition in the cartridge is preferably 40~95 weight %, more preferably 50~90 weight %.
Cartridge of the present invention so long as have getting final product of water absorbency resin composition and hydrophilic fibre, does not have particular determination to its form.
Preferred cartridge form for example can be enumerated and mix the hybrid dispersions that obtains, the laminated structure that the clamping water absorbency resin composition forms between 2 sheet hydrophilic fibres etc. for making water absorbency resin composition and hydrophilic fibre become even composition.
Described cartridge for example can form absorbent commodity by remaining between the non-perviousness sheet material of liquid perviousness sheet material and liquid.
As liquid perviousness sheet material, no particular determination can be enumerated the non-woven fabrics of air open type that fibers such as polyethylene, polypropylene, polyester constitute, spunbonded type, chemical adhesion type, needle-penetrating etc. etc.
As the non-perviousness sheet material of liquid, no particular determination can be enumerated the synthetic resin film of resins formations such as polyethylene, polypropylene, polyvinyl chloride etc.
For the kind of absorbent commodity, no particular restriction.Its typical example can be enumerated with sanitary materials such as paper nappy, sanitary towel, incontinence pad, pet with headed by the urine absorbing material etc., civil construction such as packing material with food fresh keepings such as material, dropping liquid absorption agent, refrigeration agent with material, soil with the agriculture and garden of water-keeping material etc. with article etc.
Embodiment
Below, by embodiment and comparative example the present invention is further elaborated, but the present invention is not limited to these embodiment.
And the iron level separately in absorbent resin, oxygen-containing reducing inorganic salt, organic oxidation-resistant agent and the water absorbency resin composition is the value that obtains when measuring according to preceding method.
In addition, the water absorbency resin composition that obtains in each embodiment and each comparative example and use the rerum natura of the absorbent commodity that this water absorbency resin composition obtains is estimated in accordance with the following methods.
(1) people urinates the gel stability when absorbing
The people that will take from adult man urinates 39g measures in the 100mL beaker, adds water absorbency resin composition 1g, makes the people and urinates the absorption gel.With this people urinate absorb gel and in 40 ℃ thermostatic bath, place 24 hours after, according to following judgement criteria, the stability of gel is estimated.
[judgement criteria]
◎: gel is flexible, can not break even firmly push also.
Zero: though gel is flexible, firmly push, will break.
△: gel has shape, but one pinches and will break gently.
*: the shape of gel is at random.
Gel stability when (2) physiological saline absorbs
0.9 weight % physiological saline 39g is measured in the beaker of 100mL capacity,, make physiological saline and absorb gel toward wherein adding water absorbency resin composition 1g.After this physiological saline absorbed gel place 24 hours in 40 ℃ thermostatic bath,, the stability of gel is estimated according to following judgement criteria.
[judgement criteria]
◎: gel is flexible, can not break even firmly push also.
Zero: though gel is flexible, firmly push, will break.
△: gel has shape, but one pinches and will break gently.
*: the shape of gel is at random.
(3) monitoring test
Dried the mixing of wood pulp 7g with water absorbency resin composition 13g and pulverizing is configured as long 40cm, wide 12cm size.Clamp the upper and lower of the hybrid dispersions that obtains respectively with the toilet paper of 0.5g, give overall applied load, make cartridge.
After the cartridge that commercially available hippen (L number) is inner is removed fully from the non-perviousness sheet material of liquid (back-sheet) side, insert described cartridge carefully, use adhesive tape to seal up, make the monitoring test absorbent commodity.
After allowing several children use the absorbent commodity that obtains, reclaim this absorbent commodity.
Then, in accordance with the following methods, gel fraction defective, average absorption amount and the leakage rate of the absorbent commodity after reclaiming are investigated.
A. gel fraction defective
Estimate gel is bad according to following judgement criteria, confirm as the number of the number of the bad absorbent commodity of gel divided by the absorbent commodity that reclaims, what obtain is on duty with 100, calculates the gel fraction defective.
[judgement criteria]
*: the shape of gel (it is bad to regard as gel) at random.
Zero: gel shape is not at random.
B. average absorption amount
Remove the value after the urine absorbed dose accumulative total of the absorbent commodity that reclaims with the number of the absorbent commodity that reclaims, calculate the average absorption amount.
C. leakage rate
Remove the number of the absorbent commodity that leakage is arranged with the number of the absorbent commodity that reclaims, what obtain is on duty with 100, calculates leakage rate.
(4) coloring resistance of absorbent commodity
Dried the mixing of wood pulp 7g with water absorbency resin composition 13g and pulverizing is configured as long 40cm, wide 12cm size.Clamp the upper and lower of the hybrid dispersions that obtains respectively with the toilet paper of 0.5g, give overall applying load, make cartridge.Top operating weight 20g/m from this cartridge 2Liquid infiltration type polyethylene system air open type non-woven fabrics, use the non-perviousness polyethylene sheets of liquid from the bottom of this cartridge, with this cartridge clamping, make coloring resistance test absorbent commodity.
The absorbent commodity that obtains placed 20 days in the constant temperature and humidity cabinet that is set at 50 ± 2 ℃ of temperature, relative humidity 90 ± 2% after, water absorbency resin composition in the visual observations absorbent commodity painted estimated the coloring resistance of absorbent commodity according to following judgement criteria.
[judgement criteria]
A: even remove non-woven fabrics, take cartridge apart and see, inner absorbent resin does not have painted yet.
B: when observing, can't see painted that absorbent resin causes, but remove non-woven fabrics, take cartridge apart and see, can see that a part of absorbent resin is painted from the top of non-woven fabrics.
C: observe from the top of non-woven fabrics, it is painted to see that absorbent resin causes.
Production Example 1
In five mouthfuls of round tube type round-bottomed flasks of the 1000mL capacity that possesses stirrer, reflux exchanger, dropping funnel, thermometer and nitrogen ingress pipe, add normal heptane 500mL.To wherein adding HLB is that 3.0 sucrose fatty ester [Mitsubishi Chemical's (strain) system, marque: S-370] 0.92g makes its dispersion as tensio-active agent, heats up, and makes after the surfactivity dissolving, is cooled to 55 ℃.
In addition, in the Erlenmeyer flask of 500mL capacity, add 80 weight % acrylic acid aqueous solution 92g.Cool off by external edge, the limit drip in this Erlenmeyer flask 30 weight % aqueous sodium hydroxide solution 102.2g (iron level: 0.2ppm), in and 75 moles of % of vinylformic acid, be modulated into acrylic acid part corrective.And then, add water 50.2g, polymerization starter Potassium Persulphate 0.11g and, be modulated into the monomer solution that the fs polymerization is used as the ethylene glycol diglycidylether 9.2mg of linking agent.
Under the state that stirs, the monomer solution that this fs polymerization is used all joins in above-mentioned five mouthfuls of round tube type round-bottomed flasks, make its dispersion, use nitrogen with after fully replacing in the system, heat up, make that bathing temperature remains on 70 ℃, carry out 1 hour polyreaction after, be cooled to room temperature, obtain polymerization slurry.
And then, in the Erlenmeyer flask of another one 500mL capacity, add 80 weight % acrylic acid aqueous solution 119.1g, the limit cooling, the limit drip 30 weight % aqueous sodium hydroxide solution 132.2g (iron level: 0.2ppm), in and 75 moles of % of vinylformic acid, add water 27.4g, Potassium Persulphate 0.14g and ethylene glycol diglycidylether 35.7mg, modulate the monomer solution that the subordinate phase polymerization is used, at the ice-water bath internal cooling.
After the monomer solution that this subordinate phase polymerization is used all joins in the described polymerization slurry that obtains, re-use nitrogen, heat up, make that bathing temperature remains on 70 ℃, carries out the polyreaction of 2 hours subordinate phase in the system fully after the displacement.After polyreaction finishes, from the aqueous gel shape thing that is scattered in normal heptane, by component distillation, only with moisture removal outside system.Add 2 weight % ethylene glycol diglycidylether aqueous solution 8.44g in the gelling material that obtains, further by distillation moisture and normal heptane are removed, drying obtains absorbent resin 215.5g.Iron level in this absorbent resin is 0.3ppm.
Production Example 2
In Production Example 1, except that using 30 weight % aqueous sodium hydroxide solutions (iron level: 0.5ppm) replace 30 weight % aqueous sodium hydroxide solutions (iron level: 0.2ppm), carry out the operation same, obtain absorbent resin 216.9g with Production Example 1.Iron level in this absorbent resin is 0.6ppm.
Production Example 3
In Production Example 1, except that using 30 weight % aqueous sodium hydroxide solutions (iron level: 3.3ppm) replace 30 weight % aqueous sodium hydroxide solutions (iron level: 0.2ppm), carry out the operation same, obtain absorbent resin 216.9g with Production Example 1.Iron level in this absorbent resin is 3.5ppm.
Production Example 4
In Production Example 1, except that using 30 weight % aqueous sodium hydroxide solutions (iron level: 6.5ppm) replace 30 weight % aqueous sodium hydroxide solutions (iron level: 0.2ppm), carry out the operation same, obtain absorbent resin 216.9g with Production Example 1.Iron level in this absorbent resin is 7.0ppm.
Embodiment 1
In the polythene container of 2L capacity, pack into according to absorbent resin 100 weight parts that obtain with the same method of Production Example 1, add the S-WAT big eastern chemical industry of A[(strain) system, trade name: sodium sulphite anhydrous 99.3 foodstuff additive usefulness, iron level: 1.4ppm] 2 weight parts, use the rotary mixing machine of intersection [bright and industrial (strain) system, model: CM-3], with rotational velocity 30rpm, revolution speed 30rpm polythene container was mixed 1 hour, obtain water absorbency resin composition.Iron level in this water absorbency resin composition is 0.3ppm.
The wood pulp 7g of the water absorbency resin composition 13g that obtains and pulverizing done mix, be configured as long 40cm, wide 12cm size.Clamp the upper and lower of the hybrid dispersions that obtains respectively with the toilet paper of 0.5g, give overall applying load, make cartridge.
After the cartridge that commercially available hippen (L number) is inner is removed fully from the non-perviousness sheet material of liquid (back-sheet) side, insert described cartridge carefully, use adhesive tape to seal up, make the monitoring test absorbent commodity.
Top operating weight 20g/m from this cartridge 2Liquid infiltration type polyethylene system air open type non-woven fabrics, use the non-perviousness polyethylene of liquid film-making material from the bottom of this cartridge, with this cartridge clamping, make coloring resistance test absorbent commodity.
About the rerum natura of the water absorbency resin composition that obtains, according to preceding method, to (1) people urinate the gel stability when absorbing, the gel stability when (2) physiological saline absorbs is estimated.In addition, use the monitoring test absorbent commodity, carry out aforesaid (3) monitoring test.And then, use coloring resistance test absorbent commodity, the coloring resistance of aforesaid (4) absorbent commodity is estimated.Its result is as shown in table 2.
Embodiment 2~6 and comparative example 1~3
In embodiment 1, except absorbent resin 100 weight parts that obtain in the numbering of the Production Example shown in the absorbent resin use table 1, the oxygen-containing reducing inorganic salt use outside the oxygen-containing reducing inorganic salt shown in the table 1 according to the addition shown in the table 1, other are identical with embodiment 1, obtain water absorbency resin composition thus.Iron level in the water absorbency resin composition that obtains is as shown in table 1.
In addition, Details as Follows for the oxygen-containing reducing inorganic salt of putting down in writing in table 1 and the table 3 described later.
S-WAT A: big eastern chemical industry (strain) system, trade name: the sodium sulphite anhydrous 99.3 foodstuff additive are used, iron level: 1.4ppm
S-WAT B: big eastern chemical industry (strain) system, trade name: sodium sulphite anhydrous 99.3 90, iron level: 23ppm
Sodium bisulfite A: big eastern chemical industry (strain) system, trade name: anhydrous sodium sodium pyrosulfate, iron level: 1.5ppm
Sodium bisulfite B: Northeast chemistry (strain) system, trade name: 1 grade of sodium bisulfite, iron level: 15ppm
Potassium pyrosulfite: big eastern chemical industry (strain) system, trade name: potassium pyrosulfite, iron level: 1.3ppm
V-Brite B: daily output chemical industry (strain) system, trade name: the V-Brite B foodstuff additive are used, iron level: 1.9ppm
Sodium Nitrite: daily output chemical industry (strain) system, trade name: S-WAT, iron level: 2.5ppm
Table 1
The embodiment numbering Absorbent resin The oxygen-containing reducing inorganic salt Water absorbency resin composition
Kind Iron level (ppm) Kind Iron level (ppm) Addition (weight part) Iron level (ppm)
1 Production Example 1 0.3 S-WAT A 1.4 2 0.3
2 Production Example 2 0.6 S-WAT A 1.4 2 0.6
3 Production Example 1 0.3 Sodium bisulfite A 1.5 2 0.3
4 Production Example 1 0.3 Potassium pyrosulfite 1.3 3 0.3
5 Production Example 1 0.3 V-Brite B 1.9 2 0.3
6 Production Example 1 0.3 Sodium Nitrite 2.5 2 0.3
Comparative example 1 Production Example 2 0.6 S-WAT B 23 3 1.3
2 Production Example 3 3.5 S-WAT B 23 2 3.9
3 Production Example 4 7.0 Sodium bisulfite B 15 2 7.2
(notes)
The Production Example numbering of putting down in writing in " kind " hurdle of " absorbent resin ", the absorbent resin that obtains in this Production Example is used in expression.
Then, use the water absorbency resin composition that obtains in each embodiment or each comparative example, the same with embodiment 1, make cartridge and absorbent commodity, its rerum natura is estimated.Its result is as shown in table 2.
Table 2
The embodiment numbering The people urinates the gel stability when absorbing Gel stability when physiological saline absorbs Monitoring test The coloring resistance of absorbent commodity
Reclaim number Gel fraction defective (%) Average absorption amount (g/) Leakage rate (%)
1 154 1.3 182 1.9 A
2 150 5.3 160 8.0 A
3 148 2.7 158 2.7 A
4 155 3.2 142 3.9 A
5 159 3.8 168 4.4 A
6 157 3.8 143 5.1 A
Comparative example 1 × 133 12.8 135 14.3 B
2 × 140 19.3 149 17.1 C
3 × 149 23.5 169 20.1 C
By result shown in the table 2 as can be known, according to each embodiment, even the absorbent resin amount that contains in the water-absorbing body is many, though can obtain gel for the people body fluid such as urinate stable superior hot and humid down, the water absorbency resin composition that coloring resistance is also superior.
Embodiment 7
In the polythene container of 2L capacity, pack into according to absorbent resin 100 weight parts that obtain with the same method of Production Example 1, add S-WAT [big eastern chemical industry (strain) system, trade name: the sodium sulphite anhydrous 99.3 foodstuff additive are used, iron level: 1.4ppm] 2 weight parts and L-xitix (ロ シ ユ PVC ミ Application ジ セ パ Application corporate system, trade name: L-xitix, iron level: 0.8ppm) 0.02 weight part, use the rotary mixing machine of intersection [bright and industrial (strain) system, model: CM-3], with rotational velocity 30rpm, revolution speed 30rpm mixes polythene container 1 hour, obtains water absorbency resin composition.Iron level in the gained water absorbency resin composition is as shown in table 3.
The wood pulp 7g of the water absorbency resin composition 13g that obtains and pulverizing done mix, be configured as long 40cm, wide 12cm size.Clamp the upper and lower of the hybrid dispersions that obtains respectively with the toilet paper of 0.5g, give overall applying load, make cartridge.
After the cartridge that commercially available hippen (L number) is inner is removed fully from the non-perviousness sheet material of liquid (back-sheet) side, insert described cartridge carefully, use adhesive tape to seal up, make the monitoring test absorbent commodity.
Top operating weight 20g/m from this cartridge 2Liquid infiltration type polyethylene system air open type non-woven fabrics, use the non-perviousness polyethylene of liquid film-making material from the bottom of this cartridge, with this cartridge clamping, make coloring resistance test absorbent commodity.
About the rerum natura of the water absorbency resin composition that obtains, according to preceding method, to (1) people urinate the gel stability when absorbing, the gel stability when (2) physiological saline absorbs is estimated.In addition, use the monitoring test absorbent commodity, carry out aforesaid (3) monitoring test.And then, use coloring resistance test absorbent commodity, the coloring resistance of aforesaid (4) absorbent commodity is estimated.Its result is as shown in table 4.
Embodiment 8~13 and comparative example 4~6
In embodiment 7, except absorbent resin 100 weight parts that obtain in the numbering of the Production Example shown in the absorbent resin use table 3, oxygen-containing reducing inorganic salt and organic oxidation-resistant agent are used outside oxygen-containing reducing inorganic salt shown in the table 3 and the organic oxidation-resistant agent according to the addition shown in the table 3, other are identical with embodiment 7, obtain water absorbency resin composition thus.Iron level in the water absorbency resin composition that obtains is as shown in table 3.
In addition, Details as Follows in the organic oxidation-resistant agent of putting down in writing in the table 3.
L-xitix A: ロ シ ユ PVC ミ Application ジ ャ パ Application corporate system, trade name: L-xitix, iron level: 0.8ppm
Gallic acid n-propyl A: big Japanese pharmacy (strain) system, trade name: gallic acid n-propyl foodstuff additive are used, iron level: 0.4ppm
Gallic acid n-propyl B: ミ De リ chemistry (strain) system, trade name: gallic acid n-propyl feed grade, iron level: 5.5ppm
SODIUM ISOVITAMIN C: rattan pharmaceutical industries (strain) system, trade name: SODIUM ISOVITAMIN C, iron level: 1.2ppm
2-mercaptobenzimidazole: imperial palace development chemistry (strain) system, trade name: ノ Network ラ Star Network MB, iron level: 1.8ppm
Ethyl protocatechuate: Northeast chemistry (strain) system, trade name: ethyl protocatechuate, iron level: 1.8ppm
Butyl hydroxyanisole: and the pure pharmaceutical worker's industry of light (strain) is made, trade name: butyl hydroxyanisole, iron level: 2.0ppm
L-xitix B: and the pure pharmaceutical worker's industry of light (strain) is made, trade name: 1 grade in L-xitix, iron level: 6.2ppm
Table 3
The embodiment numbering Absorbent resin The oxygen-containing reducing inorganic salt The organic oxidation-resistant agent Water absorbency resin composition
Kind Iron level (ppm) Kind Iron level (ppm) Addition (weight part) Kind Iron level (ppm) Addition (weight part) Iron level (ppm)
7 Production Example 1 0.3 S-WAT A 1.4 2 L-xitix A 0.8 0.02 0.3
8 Production Example 2 0.6 S-WAT A 1.4 2 L-xitix A 0.8 0.01 0.6
9 Production Example 1 0.3 S-WAT A 1.4 1 Gallic acid n-propyl A 0.4 0.1 0.3
10 Production Example 1 0.3 Sodium bisulfite A 1.5 2 SODIUM ISOVITAMIN C 1.2 0.05 0.3
11 Production Example 1 0.3 Potassium pyrosulfite 1.3 3 2-mercaptobenzimidazole 1.8 0.1 0.3
12 Production Example 1 0.3 V-Brite B 1.9 2 Ethyl protocatechuate 1.8 0.5 0.3
13 Production Example 1 0.3 Sodium Nitrite 2.5 2 Butyl hydroxyanisole 2.0 1 0.4
Comparative example 4 Production Example 2 0.6 S-WAT B 23 3 L-xitix B 6.2 0.02 1.3
5 Production Example 3 3.5 S-WAT B 23 2 L-xitix B 6.2 0.02 3.9
6 Production Example 4 7.0 Sodium bisulfite B 15 2 Gallic acid n-propyl B 5.5 0.1 7.2
The Production Example numbering of putting down in writing in " kind " hurdle of (notes) " absorbent resin ", the absorbent resin that obtains in this Production Example is used in expression.
Then, use the water absorbency resin composition that obtains, the same with embodiment 7, make cartridge and absorbent commodity, its rerum natura is estimated.Its result is as shown in table 4.
Table 4
The embodiment numbering The people urinates the gel stability when absorbing Gel stability when physiological saline absorbs Monitoring test The coloring resistance of absorbent commodity
Reclaim number Gel fraction defective (%) Average absorption amount (g/) Leakage rate (%)
7 165 1.2 171 1.2 A
8 170 4.7 152 5.9 A
9 159 1.9 180 1.9 A
10 151 2.6 175 2.6 A
11 152 3.3 177 3.9 A
12 159 3.1 146 4.4 A
13 159 3.8 183 5.0 A
Comparative example 4 135 11.1 153 13.3 B
5 142 17.6 148 20.4 C
6 158 20.3 159 22.2 C
By result shown in the table 4 as can be known, according to each embodiment, even the absorbent resin amount that contains in the water-absorbing body is many, can obtain gel and the stable superior of body fluid such as urinate for the people, even further the stability to aqueous electrolyte liquids such as physiological saline is also superior to hot and humid following, the water absorbency resin composition that coloring resistance is also superior.
As mentioned above, water absorbency resin composition of the present invention, even the absorbent resin amount that contains in the water-absorbing body is many, though gel for the people body fluid such as urinate stable superior hot and humid down, coloring resistance is also superior.Use this water absorbency resin composition, can access superior cartridge of these rerum naturas and absorbent commodity.
Utilize possibility on the industry
Absorber and the absorbent commodity of water absorbency resin composition of the present invention have been used, with headed by the urine absorbing material etc., can suit as civil construction such as packing materials with food fresh keepings such as material, dropping liquid absorbent, refrigeration agent with material, soil with the agriculture and garden of water-keeping material etc. with article etc. with the hygienic materials such as paper nappy, sanitary napkin, incontinence pad, pet.

Claims (9)

1. water absorbency resin composition, it contains the oxygen-containing reducing inorganic salt and absorbent resin forms, and iron level is below the 1ppm.
2. water absorbency resin composition as claimed in claim 1, wherein, the oxygen-containing reducing inorganic salt are at least a kind that is selected from sulphite, hydrosulphite, pyrosulfite, hyposulfite and the nitrite.
3. water absorbency resin composition as claimed in claim 1 or 2, wherein, the amount of oxygen-containing reducing inorganic salt is 0.01~5 weight part with respect to absorbent resin 100 weight parts.
4. as each described water absorbency resin composition of claim 1~3, wherein, further contain the organic oxidation-resistant agent.
5. water absorbency resin composition as claimed in claim 4, wherein, the organic oxidation-resistant agent is at least a kind that is selected from xitix class, saccharosonic acid class, Nutgalls acids, Protocatechuic Acid class, benzimidazoles and the alkyl hydroxy methyl-phenoxide class.
6. as claim 4 or 5 described water absorbency resin compositions, wherein, the amount of organic oxidation-resistant agent is 0.001~5 weight part with respect to absorbent resin 100 weight parts.
7. cartridge, it possesses as claim 1~6 each described water absorbency resin composition and hydrophilic fibre.
8. cartridge as claimed in claim 7, wherein, the content of water absorbency resin composition is 40~95 weight %.
9. absorbent commodity, it forms as claim 7 or 8 described cartridges by keeping between liquid perviousness sheet material and the non-perviousness sheet material of liquid.
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